The objective of this study was to develop new nanofiltration (NF) membranes capable of providing significantly greater water permeability and higher rejection of water contaminants compared to state-of-the-art NF membranes. The active layer of the new NF membranes is prepared with rigid star amphiphiles (RSAs) synthesized as part of this study. Performance characterization for a first generation of RSA membranes in a bench-scale apparatus reveals that most of the new membranes provide water permeability of 1.3-3.1 times that of two commercial NF membranes with polyamide active layers while providing comparable rejection of the organic contaminant surrogate Rhodamine WT. However, the rejection of arsenious acid (H3AsO3) by most new NF membranes was found to be lower than that by the two commercial NF membranes tested. Future research efforts of this study will focus on exploring if H3AsO3 rejection could be significantly increased, without negatively affecting water permeability and organic contaminant rejection, by addition of various chemical groups to RSA hydrophobic cores and hydrophilic branches, and by RSA cross-linking.